[W(CO)(PhC2Ph)2(η-C5HPh4)][BF4] | 241481-54-9

• 英文名称: [W(CO)(PhC2Ph)2(η-C5HPh4)][BF4]
• CAS: 241481-54-9
• 化学式: BF₄*C₅₈H₄₁OW
• 分子量: 1024.62
• InChiKey: RJBNSTSOPCUDEL-UHFFFAOYSA-N

反应信息

• 作为反应物：
  描述：

  [W(CO)(PhC2Ph)2(η-C5HPh4)][BF4] 在 [Co(η-C5H5)2] 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 生成 [W(CO)(PhC2Ph)2(η-C5HPh4)]
  参考文献：
  名称：

  Reduction of [ML(alkyne)₂(η-C₅R‘₅)]⁺ (M = Mo or W, L = MeCN or CO, R‘ = H or Me, C₅R‘₅ = C₅HPh₄):  Characterization of Radical Intermediates in the Reductive Coupling of Coordinated Alkynes

  摘要：

  The complexes [M(NCMe)(RC2R)(2)(eta-C5R5')](+) (M = Mo or W, R = Me or Ph; R' = H or Me, C5R5' = C5HPh4) undergo one-electron reduction to [M(NCMe)(RC2R)(2)(eta-C5R5')], which rapidly lose acetonitrile to give the 17-electron complexes [M(RC2R)(2)(eta-C5R5')]. The stability of [M(RC2R)(2)(eta-C5R5')] depends on R and R'; for R = Ph, the radical is sufficiently stable so that its reduction to the 18-electron anion [M(RC2R)(2)(eta-C5R5')](-) is detected in the cyclic voltammogram. Chemical reduction of [Mo(NCMe)(PhC2Ph)(2)(eta-C5HPh4)](+) with [Co(eta-C5H5)(2)] gives the air-sensitive solid [Mo(PhC2Ph)(2)(eta-C5HPh4)], characterized as an alkyne-based radical by ESR spectroscopy, which gives [Mo(NCMe)(PhC2Ph)(2)(eta-C5HPh4)](+) when treated with [Fe(eta-C5H5)(2)](+) in acetonitrile. The carbonyl cations [M(CO)(RC2R)(2)(eta-C5R5')](+) (M = Mo, Tm) undergo two sequential one-electron reductions, the first of which is reversible and gives the 19-electron species [M(CO)(RC2R)(2)(eta-C5R5')]. The 19-electron radical [Mo(CO)(PhC2Ph)(2)(eta-C5Me5)] has been characterized in solution by IR and ESR spectroscopy.

  DOI：

  10.1021/om990089l
• 作为产物：
  描述：

  四氟硼酸-二乙醚络合物 、 [W(CH3)(CO)3(η-C5HPh4)] 、 二苯基乙炔 以 二氯甲烷 为溶剂， 以64%的产率得到[W(CO)(PhC2Ph)2(η-C5HPh4)][BF4]
  参考文献：
  名称：

  Reduction of [ML(alkyne)₂(η-C₅R‘₅)]⁺ (M = Mo or W, L = MeCN or CO, R‘ = H or Me, C₅R‘₅ = C₅HPh₄):  Characterization of Radical Intermediates in the Reductive Coupling of Coordinated Alkynes

  摘要：

  The complexes [M(NCMe)(RC2R)(2)(eta-C5R5')](+) (M = Mo or W, R = Me or Ph; R' = H or Me, C5R5' = C5HPh4) undergo one-electron reduction to [M(NCMe)(RC2R)(2)(eta-C5R5')], which rapidly lose acetonitrile to give the 17-electron complexes [M(RC2R)(2)(eta-C5R5')]. The stability of [M(RC2R)(2)(eta-C5R5')] depends on R and R'; for R = Ph, the radical is sufficiently stable so that its reduction to the 18-electron anion [M(RC2R)(2)(eta-C5R5')](-) is detected in the cyclic voltammogram. Chemical reduction of [Mo(NCMe)(PhC2Ph)(2)(eta-C5HPh4)](+) with [Co(eta-C5H5)(2)] gives the air-sensitive solid [Mo(PhC2Ph)(2)(eta-C5HPh4)], characterized as an alkyne-based radical by ESR spectroscopy, which gives [Mo(NCMe)(PhC2Ph)(2)(eta-C5HPh4)](+) when treated with [Fe(eta-C5H5)(2)](+) in acetonitrile. The carbonyl cations [M(CO)(RC2R)(2)(eta-C5R5')](+) (M = Mo, Tm) undergo two sequential one-electron reductions, the first of which is reversible and gives the 19-electron species [M(CO)(RC2R)(2)(eta-C5R5')]. The 19-electron radical [Mo(CO)(PhC2Ph)(2)(eta-C5Me5)] has been characterized in solution by IR and ESR spectroscopy.

  DOI：

  10.1021/om990089l